CN102189860B

CN102189860B - Recording method of print and coloured image, lookup table and white ink

Info

Publication number: CN102189860B
Application number: CN201110031699.4A
Authority: CN
Inventors: 奥田一平; 加贺田尚义; 佐野强
Original assignee: Seiko Epson Corp
Current assignee: Seiko Epson Corp
Priority date: 2010-01-27
Filing date: 2011-01-25
Publication date: 2014-07-02
Anticipated expiration: 2031-01-25
Also published as: JP2011153225A; US20110181646A1; CN102189860A; US9782977B2; US20150091972A1

Abstract

The invention relates to a recording method of a print and a coloured image, a lookup table for recording a coloured print and the coloured image and white ink. As the evaluation of an LS value of white ink using white pigment and taking at least one polyurethane resin and other resins as fixed resin and a utilization method based on the LS value, the print having a wide colour reproduction region can be realized. Wherein an image is recorded on a transparent film by using white ink whose white shielding degree is above 50; and the white ink takes white pigment and at least one polyurethane resin as the fixed resin.

Description

Recording method, look-up table and the white ink of printed article, coloured image

Technical field

The present invention relates to have the white printed article in wide color reproduction region, to the transparent base material such as plastics (for example relate in particular to, hyaline membrane) make white printed article with white ink, and while having carried out colored printing, white printed article, the recording method of coloured image, colored printing thing, the coloured image with wide color reproduction region record the look-up table and the white ink that use.

Background technology

Ink jet recording method can record with better simply device the image of fine, has obtained in all fields development fast.In addition, application purpose is variation also, and the object based on is separately used recording medium or ink.

And then, as the evaluation index of white ink printed article that uses white ink, conventionally use L value (degree of expression based on catoptrical brightness).

In addition, used the white colorants (pigment) such as titanium oxide to improve observability in the past.But the dot matrix part of coloured image but becomes ink layer thickening, be situated between by the active energy ray of white layer irradiate cause curing carry out insufficient, by the reason becoming by generations such as the curing bad colour diffusions causing of colored ink layer.

About white ink, even known, transparent recording medium, the low recording medium of brightness are also had to good observability and the ink jet recording method of tone reproduction.(with reference to patent documentation 1)

In above-mentioned patent documentation 1, there is following record.

On printing medium, when picture with the aid of pictures, use the ink-jet printer with tone reproduction device to form white image with white ink on printing medium, on it, use colored ink to form the coloured image with contrast with erect image.

In addition, while being situated between by printing medium picture with the aid of pictures, first on printing medium, use colored ink to form the coloured image with contrast with reverted image, on it, form white image with white ink.Picture.

Now, in order to obtain good colour rendering and the contrast of coloured image, preferably penetrating concentration is more than 0.15 and the white ink layer of L value more than 65.

More preferably penetrating concentration more than 0.2 and L* value more than 70.When lower than this value or while thering is no white ink layer, between printing medium and coloured image, can not obtain contrast, cause observability variation, for low concentration region, can not get especially contrast, make image quality deteriorated.There is no the specific upper limit, but as can reach the level of high concentration in ink manufacture, penetrating concentration is below 0.5, L value is below 100.

As mentioned above, invention described in patent documentation 1, in order to obtain good colour rendering and the contrast of coloured image, more than 0.15 and L* value is more than 65 from penetrating concentration, more preferably penetrating concentration is more than 0.2 and L value is that more than 70 record can be found out, need specific penetrating concentration and L* value both for higher.

The applicant finds following opinion,, as the evaluation index of white printed article in the past, although conventionally use L* value (representing the degree of catoptrical brightness), even but the also difference of shielding (degree of screening) of the identical white printed article of L value mostly time, the kind of resin that it uses along with white ink and the difference of content and difference, and carried out applying for (Japanese Patent Application 2009-161350) with this.

Above-mentioned opinion provides new white degree of screening evaluation method,, even L* value is identical when most, the shielding of white printed article is also different these opinions for basis, use new definition as the definition of the white content of white ink printed article, be about to " white degree of screening ", with " L* value " and " integrated value of the transmissivity of visible region " numerical value that is mutually related " (L* value-α)/integrated value × 1000 " (hereinafter referred to as LS value (Lightness Shielding)), white degree of screening is evaluated.

Then, by the new white degree of screening evaluation method to evaluate white degree of screening as basis, about the example of white printed article is as describing with reference to embodiment.

Being implemented as follows of reference implementation mode.

The white degree of screening evaluation method of reference implementation mode comprises: measure the step of the L* value of white printed article, obtain the step of the transmissivity integrated value of the visible region of above-mentioned white printed article, obtained the step of white degree of screening by above-mentioned L* value and integrated value; Obtaining the white degree of screening of white printed article evaluates.

In reference implementation mode, for " white degree of screening ", the light that sees through fluorescent lamp is observed while being printed on the printed article in transparent medium with white ink, visible level with the light of fluorescent lamp is evaluated white degree of screening, will be above as 1 example, evaluate according to these six grades of AA, A, B, C, D, E.

The manufacture method of the white ink in reference implementation mode is as described below.

It is characterized in that, comprise: the step that determines the kind of colorant; Set the step of the white degree of screening of wishing; According to the numerical value of white degree of screening of setting, with reference to the regulation of storage in advance decide the step of the kind of fixing resin with the table of the relation of the corresponding fixing resin of colorant and white degree of screening.

The manufacture supportive device of the white ink in reference implementation mode is as described below.It is characterized in that, possess: the colorant kind input unit of the kind of the colorant that input is used, set the white degree of screening setting device of the white degree of screening of wishing, according to the rules fixing resin kind and white degree of screening relation table and according to the numerical value of the white degree of screening of setting, decide the device of the kind of fixing resin with reference to above-mentioned table.

1. white ink composition

1.1 colorant

White ink composition in reference implementation mode, as white colorant, for example, preferably includes metallic compound or hollow resin particle.

As the metallic compound with reference in embodiment, as long as the containing metal atomic compound that can be used as pigment use is just not particularly limited, preferably can enumerate the metal oxide, barium sulfate, the calcium carbonate that used as Chinese white in the past.As metal oxide, be not particularly limited, for example can enumerate titanium dioxide, zinc oxide, silica, aluminium oxide, magnesia etc.Metallic compound as a reference example, wherein preferred titanium dioxide, aluminium oxide.

The content of above-mentioned metallic compound is preferably 1.0～20.0 quality % of all-mass with respect to white ink composition, more preferably 5.0～10.0 quality %.When the content of metal oxide exceedes 20.0 quality %, sometimes exist and cause that ink jet type records the hole plug of shower nozzle etc. and the situation of infringement reliability.On the other hand, in the time being less than 1.0 quality %, exist the colour saturation of whiteness etc. to become not enough trend.

The average grain diameter (external diameter) of metallic compound, preferably 30～600nm, more preferably 200～400nm.When external diameter exceedes 600nm, thereby the sedimentation of particle generation sometimes etc. infringements dispersion stabilization in addition, sometimes exists and causes that ink jet type records the hole plug of shower nozzle etc. and the situation of infringement reliability.On the other hand, in the time that external diameter is less than 30nm, exist the colour saturation of whiteness etc. to become not enough trend.

The average grain diameter of metallic compound can utilize the particle size distribution device using laser diffraction and scattering method as measuring principle to measure.As laser diffraction formula particle size distribution device, for example, can use the size distribution (for example, " Microtrac UPA " Nikkiso Company Limited's system) take dynamic light scattering method as measuring principle.

As the hollow resin particle with reference in embodiment, preferably there is cavity therein, its shell is to be formed by the resin with liquid permeability.According to this structure, in the time that hollow resin particle exists in aqueous ink composition, inner cavity is filled up by aqueous medium.Filled up the particle of aqueous medium, owing to having and almost equal proportion of outside aqueous medium, so can be in aqueous ink composition not sedimentation and keep dispersion stabilization.Thus, can improve storage stability, the ejection stability of white ink composition.

In addition, while making white ink composition containing hollow resin particle be ejected on paper, other recording medium, because the aqueous medium of inside particles is removed and forms cavity when dry.By containing air at inside particles, particle forms different resin bed and the air layers of refractive index, makes incident light scattering effectively, therefore can present white.Should illustrate, painted to the resin bed of formation hollow resin particle by the state with residual light permeability, also can present white color in addition.

The hollow resin particle using in reference implementation mode, there is no particular limitation, can use known thing.For example, the hollow resin particle of recording in the description of No. 3562754th, can preferably use United States Patent (USP) No. 4880465, patent etc.

Preferably 0.2～1.0 μ m of the average grain diameter (external diameter) of hollow resin particle, more preferably 0.4～0.8 μ m.When external diameter exceedes 1.0 μ m, sometimes because particle generation sedimentation etc. damages dispersion stabilization, sometimes exist in addition and cause that ink jet type records the hole plug of shower nozzle etc. and the situation of infringement reliability.On the other hand, in the time that external diameter is less than 0.2 μ m, exist the colour saturation of whiteness etc. to become not enough trend.In addition, suitable is that internal diameter is 0.1～0.8 μ m left and right.

The average grain diameter of hollow resin particle can utilize the particle size distribution device using laser diffraction and scattering method as measuring principle to measure.As laser diffraction formula particle size distribution device, for example, can use the size distribution (for example, " Microtrac UPA " Nikkiso Company Limited's system) take dynamic light scattering method as measuring principle.

The content (solid constituent) of above-mentioned hollow resin particle is preferably 5～20 quality % of all-mass with respect to white ink composition, more preferably 8～15 quality %.When the content (solid constituent) of hollow resin particle exceedes 20 quality %, sometimes exist and cause that ink jet type records the hole plug of shower nozzle etc. and the situation of infringement reliability.On the other hand, while being less than 5 quality %, exist the colour saturation of whiteness etc. to become not enough trend.

The preparation method of above-mentioned hollow resin particle, is not particularly limited, and can be suitable for known method.As the preparation method of hollow resin particle, for example, can use by vinyl monomer, surfactant, polymerization initiator and water system dispersion solvent are heated while stirring under nitrogen environment, thus the so-called emulsion polymerization method of formation hollow resin particle emulsion.

As vinyl monomer, can enumerate nonionic list ethylene unsaturated monomers, for example, can enumerate styrene, vinyltoluene, ethene, vinyl acetate, vinyl chloride, vinylidene chloride, acrylonitrile, (methyl) acrylamide, (methyl) acrylate etc.Can enumerate methyl acrylate, methyl methacrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, 2-hydroxyethyl methacrylate, (methyl) 2-EHA, (methyl) benzyl acrylate, (methyl) lauryl acrylate, (methyl) acrylic acid oil alkene ester, (methyl) acrylic acid palm ester, (methyl) stearyl acrylate base ester etc. as (methyl) acrylate.

In addition, as vinyl monomer, can use difunctionality base vinyl monomer.As difunctionality base vinyl monomer, for example, can enumerate divinylbenzene, allyl methacrylate, ethylene glycol dimethacrylate, 1,3-BDO dimethylacrylate, diethylene glycol dimethylacrylate, trimethylol-propane trimethacrylate etc.By above-mentioned monofunctional vinyl monomer and the copolymerization of above-mentioned difunctionality base vinyl monomer are cross-linked to heavens, can obtain not only possessing light scattering characteristic, also have the hollow resin particle of the characteristics such as heat resistance, solvent resistance, solvent dispersiveness.

As surfactant, as long as form the material of micelle equimolecular aggregate in water, for example, can enumerate anionic surfactant, nonionic surfactant, cationic surfactant, amphoteric surfactant etc.

As polymerization initiator, can use water-soluble known compound, for example, can enumerate hydrogen peroxide, potassium peroxydisulfate etc.

As water system dispersant, for example, can enumerate water, the water that contains hydrophilic organic solvent etc.

1.2 fixing resin

The white ink composition of reference implementation mode is preferably containing the fixing resin that is useful on fixing colorant.

As this fixing resin, as long as transparent resin is not particularly limited, can enumerate acrylic acid phenylethylene resin series, polyurethane series resin, acrylic resin, phenylethylene resin series, polyethylene-based resin, wax.Wherein, for higher white degree of screening optimization polyurethane is resin, the particularly preferably aliphatic polyurethane resin of carbonic ester system or ether system.

As the polyurethane resin with reference in embodiment, can use any pattern of the solution-type existing with the state dissolving in the emulsifying with granular dispersion, solvent in solvent.In addition, emulsifying can be categorized as forced emulsification type and self-emulsifying type according to its emulsification method, in the present invention, can use any pattern, but preferred self-emulsifying type.This is the decentralization due to self-emulsifying type, is making excellence aspect film, resistance to water compared with forced emulsification type.

While applying above-mentioned emulsifying as polyurethane resin, the average grain diameter of polyurethane resin is preferably 50～200nm, more preferably 60～200nm.If the average grain diameter of the resin of polyurethane in above-mentioned scope, can make polyurethane resin particle disperse equably in white ink composition.

The content (solid constituent) of above-mentioned polyurethane resin, with respect to preferably 0.5～10 % by weight of gross weight of ink composite, more preferably 0.5～5 % by weight.If the content of polyurethane resin exceedes 10 % by weight, sometimes damage the reliability (hole plug, ejection stability etc.) of ink, sometimes can not get the suitable physical property (viscosity etc.) as ink.On the other hand, if be less than 0.5 % by weight, the stationarity of the ink on recording medium is unexcellent, can not form the image of erasibility excellence.

1.3 permeability organic solvents

The white ink composition of reference implementation mode, preferably contains and is selected from alkane glycol and glycol ether at least a kind.Alkane glycol, glycol ether can improve the wettable of the face that is recorded to recording medium etc., thereby improve the permeability of ink.

As alkane glycol, preferably 1,2-butanediol, 1,2-pentanediol, 1,2-hexylene glycol, 1,2-heptandiol, 1, the carbon number of 2-ethohexadiol etc. is 4～8 1,2-alkane glycol.Wherein, carbon number is 6～8 1,2-hexylene glycol, 1, and 2-heptandiol, 1,2-ethohexadiol is due to high especially to the permeability of recording medium, so more preferably.

As glycol ether, can enumerate the lower alkyl ether of the polyalcohol of ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, TC, diethylene glycol single-butyl ether, DPGME, dihydroxypropane single-ethyl ether, triethylene glycol monomethyl ether, triethylene glycol single-butyl ether, tripropylene glycol monomethyl ether etc.Wherein, while using triethylene glycol single-butyl ether, can obtain the good quality that records.

The content of at least a kind that is selected from these alkane glycol and glycol ether is preferably 1～20 quality % of all-mass with respect to white ink composition, more preferably 1～10 quality %.

1.4 surfactant

It is surfactant or polysiloxane series surfactant that the white ink composition of reference implementation mode preferably contains acetylenediol.Acetylenediol is the wettable that surfactant or polysiloxane series surfactant can improve the face that is recorded to recording medium etc., thereby improves the permeability of ink.

Be surfactant as acetylenediol, for example, can enumerate 2,4,7,9-tetramethyl-5-decine-4,7-glycol, 3,6-dimethyl-4-octyne-3,6-glycol, 3,5-dimethyl-1-hexin-3 alcohol, 2,4-dimethyl-5-hexin-3-alcohol etc.In addition, acetylenediol is that surfactant can use commercially available product, for example, can enumerate OLFINE E1010, STG, Y (more than, Xin chemical company system), Surfynol 104,82,465,485, TG (more than, Air Products and Chemicals Inc. system).

As polysiloxane series surfactant, can use commercially available product, for example, can enumerate BYK-347, BY K-348 (BYK CHEM JAPAN company system) etc.

The white ink composition of reference implementation mode in addition, can contain other the surfactant such as anionic surfactant, nonionic surfactant, amphoteric surfactant.

The content of above-mentioned surfactant is preferably 0.01～5 quality % of all-mass with respect to white ink composition, more preferably 0.1～0.5 quality %.

1.5 polyalcohol

The white ink composition of reference implementation mode preferably contains polyalcohol.In the time that white ink composition of the present invention is used for to inkjet recording device, the ink jet type that is dried, prevents that polyalcohol can suppress ink records the hole plug of the ink of shower nozzle part.

As polyalcohol, for example, can enumerate ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, propane diols, butanediol, 1,2,6-hexanetriol, thioglycol, hexylene glycol, glycerine, trimethylolethane, trimethylolpropane etc.

The content of above-mentioned polyalcohol is preferably 0.1～30 quality % of all-mass with respect to white ink composition, more preferably 0.5～20 quality %.

1.6 tertiary amine

The white ink composition of reference implementation mode preferably contains tertiary amine.Tertiary amine has the function of pH adjusting agent, can easily regulate the pH of white ink composition.

As tertiary amine, for example, can enumerate triethanolamine etc.

The content of above-mentioned tertiary amine is preferably 0.01～10 quality % of all-mass with respect to white ink composition, more preferably 0.1～2 quality %.

1.7 solvents and additive

The white ink composition of reference implementation mode, contains water as usual solvents.Preferably use pure water or the ultra-pure waters such as ion exchange water, ultrafiltration water, reverse osmosis water, distilled water as water.Particularly these water are carried out to the water of sterilization treatment through ultraviolet ray irradiation or interpolation hydrogen peroxide etc., the generation of mould fungus inhibition, bacterium chronically, thereby preferably.

The white ink composition of reference implementation mode, as required, can contain the additive of antioxidant ultra-violet absorber, chelating agent, the oxygen absorbent etc. such as the mould inhibitor such as fixative, sodium benzoate anticorrisive agent, allophanate class of water-soluble rosin etc.These additives can a kind use separately, two or more can certainly be used in combination.

1.8 preparation method

The white ink composition of reference implementation mode can be used known device in the past, and for example, ball mill, puddle mixer, grater, basket type sand grinding machine (BASKET MILL), rolls etc., similarly prepare with pigment ink in the past.In the preparation, preferably use molecular filter or filter screen etc. to remove oversize grain.

The white ink composition of reference implementation mode, can form white image by being coated on various recording mediums.As recording medium, for example, can enumerate paper, ground paper, fibre, sheet material or film, plastics, glass, pottery etc.

The white ink composition of reference implementation mode, its purposes is not particularly limited, and goes for various ink-jet recordings.As ink-jet recording, for example, can enumerate the jet-propelled ink-jet of heating power, piezoelectric ink jet, continous inkjet, roll-type application (roller application), jet printing type application (spray application) etc.

Utilize the flow chart of Fig. 1, to obtaining the white degree of screening of white printed article of reference implementation mode and the basic operation of 1 example of the reference example of the white degree of screening evaluation method evaluated describe.

Measure the L* value with the white printed article of white ink printing.(step S1) obtains the transmissivity integrated value of the visible region of above-mentioned white printed article.(step S2) obtains white degree of screening by the L* value of trying to achieve in step S1 and S2 and integrated value.(step S3)

The mensuration of L* value is to use commercially availablely using the black colorimeter as substrate, and for example Gretag Macbeth Spetroscan and Spectrolino (X-Rite company system), print, colour examining.

For white printing, described white ink composition is filled in the purple storehouse (violetchamber) of special print cartridge of ink-jet printer (" PX-G930 " SEIKO EPSON Co., Ltd. system).The ink cartridge of making is like this installed to printer, has carried out printing test.

Then, export with the resolution ratio of 1440 × 720dpi for Lumirror S10-100 μ m (TORAY company system).

In this reference example, " duty " refers to the value calculating in following formula.

Count/(vertical resolution ratio × horizontal resolution ratio) × 100 of duty (%)=real lettering

(in formula, " real lettering is counted " is that the real lettering of unit are is counted, and " vertical resolution ratio " and " horizontal resolution ratio " are respectively the resolution ratio of unit are.100%duty refers to the monochromatic maximum ink quality to pixel.)

In addition, the integration of the transmissivity of sample white printed article is the integrated value of the transmissivity of (for example, 380nm～700nm) in visible region.Should illustrate, in reference example, use the wave-length coverage of afore mentioned rules, but also can be the wave-length coverage of other regulation in visible region, at that time, as long as make other corresponding relation of LS value and reference level also different from reference example.

The integrated value of transmissivity is obtained according to following method in reference example.

By the light transmitted through sample white printed article, utilize spectrophotometer to visible region (in the present invention, 380nm～700nm) measure value (unit the is %) output by the value of measuring with 0～100 scope with each wavelength at 1nm interval.

By the value of mensuration is carried out to integration, thereby obtain the integrated value (following, referred to as integrated value) of transmissivity.

The integrated value obtaining is the numerical value of 0～32000, is 0, is 32000 when transmission completely while shielding completely.

In said determination, can use spectrophotometer to measure, also can obtain by the mensuration of measuring the reflectivity obtaining based on reflection-type.

The formula of being obtained white degree of screening by L* value and integrated value is as follows.

White degree of screening (LS value)=(L* value-α)/integrated value × 1000

Wherein, from L* value, deducting α is the impact of the variable quantity of the L* value in order to improve white portion, and above-mentioned α is predefined numerical value (numerical value of 60～70), preferably " 65 ", but might not be this numerical value, can use other numerical value.

In reference example, whether the evaluation of the white degree of screening (LS value) of trying to achieve in step S3 by with judging more than the numerical value of regulation.

That is, white degree of screening is set as to the multiple ranks corresponding with the result of the visual sensory evaluation based on observer (AA, A, B, C, D, E), the numerical value of the white degree of screening corresponding with each rank is set according to actual measurement.

The benchmark (degree) of above-mentioned rank (AA, A, B, C, D, E) is as described below.

White degree of screening E: while seeing through the light observation of fluorescent lamp, there is no white printed article, fully see the degree of the light of fluorescent lamp

White degree of screening D: when the light that sees through fluorescent lamp is observed, adularescent printed article but can be clear that the degree of the light of fluorescent lamp

White degree of screening C: when the light that sees through fluorescent lamp is observed, can be clear that the light of fluorescent lamp but fuzzy slightly degree

White degree of screening B: when the light that sees through fluorescent lamp is observed, can see the light of fluorescent lamp but quite fuzzy degree

White degree of screening A: while seeing through the light observation of fluorescent lamp, almost can't see the degree of the light of fluorescent lamp

White degree of screening AA: while seeing through the light observation of fluorescent lamp, can't see the degree of the light of fluorescent lamp completely

In this reference example, according to following explanation, but might not be this numerical value by the white degree of screening of rank (AA, A, B, C, D, E) (LS value) threshold value.In addition, based on utilize the visual sensory evaluation of observer result and rank be also also nonessentially defined in above-mentioned 6 kinds of ranks.

White degree of screening E is transparent medium (without white printed article)

White degree of screening D is that LS value is greater than the 0 white printed article that is less than 54

White degree of screening C is the white printed article of LS value more than 54

White degree of screening B is the white printed article of LS value more than 64

White degree of screening A is the white printed article of LS value more than 82

White degree of screening AA is the white printed article of LS value more than 87

Then, the manufacture method of the white ink composition that at least contains colorant and fixing resin to this reference example describes.

The feature of the manufacture method of the white ink composition of this reference example is to use to possess colorant kind input unit, white degree of screening setting device, store the memory portion having stipulated with the table of the relation of the corresponding fixing resin kind of above-mentioned colorant and white degree of screening, and the white ink of calculation handling part is manufactured supportive device, comprise: the step that determines colorant kind, set the step of the white degree of screening of wishing, according to the numerical value of the white degree of screening of setting, with reference to the regulation of storage in advance decide the step of the kind of fixing resin with the form of the relation of the corresponding fixing resin of colorant and white degree of screening.

Then, the representational reference example in reference implementation mode is described.

(table 1) expression of Fig. 2, the evaluation of above-mentioned white degree of screening (LS value) becomes the typical example of multiple ranks (AA, A, B, C, D, E).

In Fig. 4, be to use titanium dioxide and hollow resin (also comprising the situation that does not use colorant) as colorant, use representational acrylic acid phenylethylene resin series (BASF AG's system " JONCRYL 62J " as fixing resin, polyurethane resin A: the company's system " D-6300 " of refining large day, polyurethane resin B: the company's system " D-6455 " of refining large day, polyurethane resin C: the company's system " D-2020 " of refining large day) reference example of (also comprising the situation that does not use fixing resin).

The comparative example (reference example) 1 of Fig. 2, is the situation (only recording medium PET) that does not use colorant and fixing resin, can not measure L value, thus integrated value because the basic transmission of light is 12136, LS value is 0, the evaluation of degree of screening is E.

Comparative example (reference example) the 2nd, uses titanium dioxide 10 (quality %) as colorant, do not use fixing resin, surfactant is 1 quality %, propane diols is 2 quality %, 1,2-hexylene glycol is 5 quality %, and 2-Pyrrolidone is 2 quality %, surplus is the situation of water, L value is 70.3, integrated value is 1113.9, LS value is 4.7, degree of screening be evaluated as D.Should illustrate, find out from the result of reference example 2, even if use titanium dioxide as colorant, but be that while not containing the white ink of fixing resin, degree of screening will be significantly deteriorated compared with containing the white ink of fixing resin.

Thus, while expecting the high white ink of white degree of screening, preferably use the white ink that contains titanium dioxide and fixing resin.

On the other hand, reference example 1-1 uses TiO 2 particles 10 (quality %) as colorant, use acrylic acid styrene resin (: BASF AG's system " JONCRYL62J ") 4 (quality %) as fixing resin, surfactant is 1 quality %, and propane diols is 2 quality %, 1,2-hexylene glycol is 5 quality %, 2-Pyrrolidone is 2 quality %, the situation that surplus is water, L value is 76.8, integrated value is 194.3, LS value is 60, degree of screening be evaluated as C.

In addition, reference example 2-1 uses TiO 2 particles 10 (quality %) as colorant, use polyurethane resin (A: the company's system " D6300 " of refining large day) 4 (quality %) as fixing resin, surfactant is 1 quality %, and propane diols is 2 quality %, 1,2-hexylene glycol is 5 quality %, 2-Pyrrolidone is 2 quality %, the situation that surplus is water, L value is 74.8, integrated value is 151.76, LS value is 64, degree of screening be evaluated as B.

In addition, reference example 3-1 uses TiO 2 particles 10 (quality %) as colorant, use polyurethane resin (B: the company's system " D6455 " 4 (quality %) of refining large day as fixing resin, surfactant is 1 quality %, and propane diols is 2 quality %, 1,2-hexylene glycol is 5 quality %, 2-Pyrrolidone is 2 quality %, the situation that surplus is water, L value is 75.3, integrated value is 119.17, LS value is 86, degree of screening be evaluated as A.

In addition, reference example 4-1 uses titanium dioxide 10 (quality %) as colorant, use polyurethane resin (C: the company's system " D2020 " 4 (quality %) of refining large day as fixing resin, surfactant is 1 quality %, and propane diols is 2 quality %, 1,2-hexylene glycol is 5 quality %, 2-Pyrrolidone is 2 quality %, the situation that surplus is water, L value is 74.9, integrated value is 102.45, LS value is 96, degree of screening be evaluated as AA.

In addition, reference example 5 is to use hollow resin 10 (quality %) as colorant, use polyurethane resin (B: the company's system " D6455 " 4 (quality %) of refining large day as fixing resin, surfactant is 1 quality %, and propane diols is 2 quality %, 1,2-hexylene glycol is 5 quality %, 2-Pyrrolidone is 2 quality %, the situation that surplus is water, L value is 78.5, integrated value is 194.5, LS value is 69, degree of screening be evaluated as B.

From the result of Fig. 2 be appreciated that when use TiO 2 particles as colorant, use polyurethane resin during as fixing resin, although because the kind LS value of polyurethane resin exists difference, LS value excellence on the whole.

In addition, in the time using hollow resin particle as colorant, L value is high, is not so good as its height but compare LS value with the situation of identical use polyurethane resin.

Then be, that the situation of other reference example of same levels is shown in Fig. 3,4,5 by there is the degree of screening (evaluation) of LS value and the reference example of Fig. 2.

(table 2) of Fig. 3 is other the reference example that is B as the degree of screening (evaluations) of the resin example 2-1 of Fig. 2, the situation that uses respectively W635 (reference example 2-2), AQ515 (reference example 2-3) and W605 (reference example 2-4) 4 quality % as fixing resin, remaining condition is identical with reference example 2-1.

(table 3) of Fig. 4 is other the reference example that is A as the degree of screening (evaluations) of the resin example 3-1 of Fig. 2, the situation that uses respectively WS6021 (reference example 3-2) 4 quality % as fixing resin, remaining condition is identical with reference example 2-1.

(table 4) of Fig. 5 is other the reference example that is AA as the degree of screening (evaluations) of the resin example 4-1 of Fig. 2, the situation that uses respectively D4200 (reference example 4-2) and WS5000 (reference example 4-3) 4 quality % as fixing resin, remaining condition is identical with reference example 2-1.

Prior art document

Patent documentation

Patent documentation 1: TOHKEMY 2003-182061 communique

Summary of the invention

In above-mentioned reference example, as shown in Figure 2, to use titanium dioxide and hollow resin (also comprising the situation that does not use colorant) as colorant, use representational acrylic acid phenylethylene resin series (BASF AG's system " JONCRYL 62J ", polyurethane resin A: the company's system " D-6300 " of refining large day, polyurethane resin B: the company's system " D-6455 " of refining large day, polyurethane resin C: the company's system " D-2020 " of refining large day) as the fixing resin example of (also comprising the situation that does not make fixing resin), but fixing resin only uses a kind of resin (being polyurethane resin substantially), evaluation and the utilizability thereof of the LS value that uses the situation of various kinds of resin as fixing resin are not done further to resolve.

Problem of the present invention (object) is, as to use titanium dioxide or hollow resin as colorant, be the basic method of utilizing by the polyurethane resin of at least a kind and other resin the evaluation and the LS value thereof that are used as the LS value of the white ink in the situation of fixing resin, realization has the printed article in wide color reproduction region.

In addition, be also to realize the coloured image that has used printed article recording method, colored printing thing, coloured image record look-up table used and the white ink for printed article.

In order to reach the printed article of the present invention of above-mentioned purpose, it is characterized in that, with white degree of screening be more than 50 white ink by recording image in hyaline membrane, described white ink uses white colorant, and uses the polyurethane resin of at least a kind as fixing resin.

In addition, in order to reach the printed article of the present invention of above-mentioned purpose, it is characterized in that, with white degree of screening be more than 50 white ink by recording image in hyaline membrane, described white ink uses white colorant, and and with the resin beyond the polyurethane resin of at least a kind and polyurethane as fixing resin.

In addition, it is characterized in that, the resin beyond above-mentioned polyurethane is at least acrylic acid styrene resin.

In addition, it is characterized in that, the resin beyond above-mentioned polyurethane is at least polyvinyl resin.

In addition, it is characterized in that, above-mentioned white degree of screening is more than 70.

In addition, it is characterized in that above-mentioned white degree of screening is " (L* value-65)/integrated value × 1000 ".

Wherein, integrated value is to be the integrated value of the transmissivity in 380nm～700nm at wavelength.

A kind of recording method, is characterized in that, when recording colour ink forms on the image of above-mentioned printed article coloured image, carries out the record of coloured image with reference to the look-up table of the white ink of the white degree of screening corresponding to regulation or regulation.

A kind of look-up table, uses during according to the above-mentioned recording method coloured image that recording colour ink forms on the image of printed article.

A kind of white ink, is characterized in that, uses white colorant, and and with the resin beyond polyurethane resin and the polyurethane of at least a kind as fixing resin, the white degree of screening on hyaline membrane when document image is more than 50.

Based on using white colorant, and and with the polyurethane resin of at least a kind and other resin as evaluation and the LS value thereof of the LS value of the white ink under the situation of fixing resin, can realize the printed article with wide color reproduction region.

In addition, can realize look-up table that the record of recording method, colored printing thing, the coloured image of the coloured image that has used printed article uses and the white ink for printed article.

Accompanying drawing explanation

Fig. 1 is the flow chart of the basic operation of 1 example of the reference example of the white degree of screening of the explanation printed article of obtaining reference implementation mode and the white degree of screening evaluation method evaluated.

Fig. 2 is the table 1 that represents the typical example that is evaluated as multiple ranks (AA, A, B, C, D, E) of white degree of screening (LS value).

Fig. 3 is the table 2 that the degree of screening (evaluation) of the resin example 2-1 of presentation graphs 2 is other reference example of B.

Fig. 4 is the table 3 that the degree of screening (evaluation) of the resin example 3-1 of presentation graphs 2 is other reference example of A.

Fig. 5 is the table 4 that the degree of screening (evaluation) of the resin example 4-1 of presentation graphs 2 is other reference example of AA.

Fig. 6 represents that the embodiment 1～4 of white degree of screening (LS value) more than 50 and white degree of screening (LS value) are less than the table 5 of the measured value of the colour gamut of 50 comparative example 1,2.

The figure that the gamut differences of the comparative example 2 that the embodiment 1 that Fig. 7 is is 53 to LS value and LS value are 27 describes.

The figure that the gamut differences of the example of Fig. 8 to L value basic identical (74.9 and 74.8), integrated value different (136 and 364) describes.

Fig. 9 is the figure that the gamut differences of the example to integrated value basic identical (136 and 132), L value different (74.9 and 75.7) describes.

Figure 10 represents LS value (white degree of screening), and corresponding a with it, b value and black (K), the figure of the relation between the OD value of blue or green (C) pinkish red (M), Huang (Y).

The specific embodiment

Embodiment

The condition determination of the table 5 of Fig. 6 of embodiments of the invention is same with reference example, as described below.The mensuration of L* value be use commercially available using the black colorimeter as substrate, for example Gretag Macbeth Spetroscan and Spectrolino (X-Rite company system) print, colour examining.

For white printing, described white ink composition is filled in the purple storehouse of special print cartridge of ink-jet printer (" PX-G930 " SEIKO EPSON Co., Ltd. system).The ink cartridge of making is like this installed to printer, has carried out printing test.

Then, export for Lumirror S10-100 μ m (TORAY company system) the resolution ratio of 1440 × 720dpi.

The integrated value of transmissivity is similarly to obtain by following method with reference example.

White degree of screening (LS value)=(L* value-α)/integrated value × 1000

Wherein, from L* value, deducting α is the impact of the variable quantity of the L* value in order to improve white portion, and above-mentioned α is predefined numerical value (numerical value of 60～70), is " 65 " in embodiment.

In addition, " the Gamut Volume " of the table 5 of Fig. 6 is volumes of the three-dimensional colour gamut of Lab (Gamut).

Carry out by the following method the mensuration of colour gamut.

The special output pattern being formed by 400 fragments with colored ink printing on aforesaid sample white printed article, the fragments all to printed article carry out colour examining, utilize calculation instrument to calculate the volume in the 3d space of L*a*b*.The Gumat Volume calculating is nondimensional.

Then, the representational embodiment to embodiments of the present invention (measuring example) describes.Fig. 6 (table 5) represents, white degree of screening (LS value) is the measured value that more than 50 embodiment 1～4 and white degree of screening (LS value) are less than the colour gamut of 50 comparative example 1,2.

In Fig. 6, use titanium dioxide (also comprising the situation that does not use colorant) as colorant, use the resin (resin B: acrylic acid styrene resin, BASF AG's system " JONCRYL62J ", resin C: polyvinyl resin, Mitsui Chemicals (strain) company's system " S120 ") beyond polyurethane resin (Resin A: Mitsui Chemicals polyurethane (strain) company's system " W605 ") and polyurethane as fixing resin.Should illustrate, beyond these, can also use TaiseiFine Chemical company system " WBR-022U ", Mitsui Wu Tian chemical company system " W635 ", the above-mentioned company's system " D-6300 " " D-6455 " " D-2020 " etc. of refining large day as polyurethane resin.As the resin beyond polyurethane, BASF AG's system " JONCRYL511 " " JONCRYL711 " " JONCRYL7001 " etc. can be used as acrylic acid styrene resin, above-mentioned BYK CHEM JAPAN company's system " AQ515 ", company of eastern nation chemistry (strain) system " Hytec E-7025P " " Hytec E-2213 " etc. can be used as polyvinyl resin.

The measured value of the comparative example 1 of the table 5 of Fig. 6, belongs to the situation (only recording medium PET) that does not use colorant and fixing resin, can not measure L value, thus integrated value due to light almost transmission be that 16136, LS value is 0, colour gamut value is 560.

The ink of comparative example 2 is to use titanium dioxide 10 (quality %) as colorant, do not use polyurethane resin A as fixing resin, and contain resin B and each 2 (the quality %) of resin C beyond polyurethane resin, contain in addition surfactant 1 (quality %), propane diols 2 (quality %), 1,2-hexylene glycol 5 (quality %), 2-Pyrrolidone 2 (quality %), remainder is made up of water.

The measured value of comparative example 1 is, L value is 74.8, integrated value is 364, LS value is 27, colour gamut value is 378160.

The ink of embodiment 1 is to use titanium dioxide 10 (quality %) as colorant, resin B (acrylic acid styrene resin) and each 1 (the quality %) of resin C (polyvinyl resin) beyond polyurethane resin A, the polyurethane resin that contains 1 (quality %) as fixing resin, contain in addition surfactant 1 (quality %), propane diols 2 (quality %), 1,2-hexylene glycol 5 (quality %), 2-Pyrrolidone 2 (quality %), remainder is made up of water.

The measured value of embodiment 1 is, L value is 75.9, integrated value is 207, LS value is 53, colour gamut value is 400360.

The ink of embodiment 2 is to use titanium dioxide 10 (quality %) as colorant, contain respectively resin B beyond the polyurethane resin A, polyurethane resin of 2 (quality %) and each 2 (the quality %) of resin C as fixing resin, contain surfactant 1 (quality %), propane diols 2 (quality %), 1 in addition, 2-hexylene glycol 5 (quality %), 2-Pyrrolidone 2 (quality %), remainder is made up of water.

The measured value of embodiment 2 is, L value is 74.9, integrated value is 136, LS value is 73, colour gamut value is 421936.

The ink of embodiment 3 is to use titanium dioxide 10 (quality %) as colorant, the resin C of the resin B, 1 (quality %) beyond the polyurethane resin of the polyurethane resin A, 2 (quality %) that contains 2 (quality %) as fixing resin, contain in addition surfactant 1 (quality %), propane diols 2 (quality %), 1,2-hexylene glycol 5 (quality %), 2-Pyrrolidone 2 (quality %), remainder is made up of water.

The measured value of embodiment 3 is, L value is 74.6, integrated value is 128, LS value is 75, colour gamut value is 424320.

The ink of embodiment 4, as colorant use titanium dioxide 10 (quality %), resin C beyond the polyurethane resin of polyurethane resin A, 4 (quality %) that contains 2 (quality %) as fixing resin, contain in addition surfactant 1 (quality %), propane diols 2 (quality %), 1,2-hexylene glycol 5 (quality %), 2-Pyrrolidone 2 (quality %), remainder is made up of water.

The measured value of embodiment 4 is, L value is 75.7, integrated value is 132, LS value is 81, colour gamut value is 444832.

Then with Fig. 7, be, that 53 embodiment 1 and LS value are that the gamut differences of 27 comparative example 2 describes to LS value of the present invention.

Fig. 7 represents, the color rendering region in the ab region while cutting with the three-

dimensional L value

10,20,30,40,50,60,70,80,90 of Lab.

While being appreciated that from Fig. 7 the white ink that use LS value is 53, compared with using the situation of the white ink that LS value is 27, there is wider color rendering region.

Then,, with Fig. 8, the embodiment that is 73 to the LS value of the present invention of the example as L value almost identical (74.9 and 74.8), integrated value different (136 and 364) 2 describes with the gamut differences of the comparative example 2 that LS value is 27.

Fig. 8 represents, the color rendering region in ab region when the cutting with the three-

dimensional L value

10,20,30,40,50,60,70,80,90 of Lab of the comparative example 2 that the embodiment 2 that LS value is 73 and LS value are 27.

While being appreciated that from Fig. 8 the white ink that use LS value is 73, compared with using the situation of the white ink that LS value is 27, there is wider color rendering region.

Then,, with Fig. 9, the gamut differences of the embodiment 4 that the embodiment 2 that is 73 to the LS value of the present invention of the example as integrated value almost identical (136 and 132), L value different (74.9 and 75.7) and LS value are 81 describes.

Fig. 9 represents, the color rendering region in ab region when the cutting with the three-

dimensional L value

10,20,30,40,50,60,70,80,90 of Lab of the embodiment 4 that the embodiment 2 that LS value is 73 and LS value are 81.

While being appreciated that from Fig. 9 the white ink that use LS value is 81, compared with using the situation of the white ink that LS value is 73, there is wider color rendering region.

Be appreciated that for being that more than 50 white ink records for white white printed article by LS value to there is excellent wider color reprodubility from the example of the colour gamut of Fig. 7～Fig. 9.

Can be understood as in addition no matter L value and integrated value poor, record white white printed article with the large white ink of LS value, there is the wider color reprodubility of excellence.

The LS value (white degree of screening) and the corresponding a of difference of reference example 2 of the present invention, embodiment 1, embodiment 2, embodiment 4 in the table of Figure 10, are shown, the relation between the OD value of b value and black (K), blue or green (C), pinkish red (M), yellow (Y).

Even be appreciated that from the table of Figure 10 LS value is 27～81 change so significantly, OD value does not show larger variation.

The mensuration of OD value is as above-mentioned, uses commercially availablely using the black colorimeter as substrate, and for example Gretag Macbeth Spetroscan and Spectrolino (X-Rite company system) print, colour examining.

For white printing, described white ink composition is filled in the purple storehouse of special print cartridge of ink-jet printer (" PX-G930 " SEIKO EPSON Co., Ltd. system).The ink cartridge of making is like this installed to printer and prints test.

Then, export with the resolution ratio of 1440 × 720dpi for Lumirror S10-100 μ m (TORAY company system).Then, on the sample after output white ink, with the single color printing fragment of all kinds of colored ink (black (K), blue or green (C), pinkish red (M) and yellow (Y)), measure the OD value of fragment.

Should illustrate, for the printing of the colored ink during for the mensuration of above-mentioned colour gamut and the mensuration of OD value, be fill respectively colored ink of all kinds in each black, blue or green, pinkish red, yellow ink storehouse of the special print cartridge of ink-jet printer (" PX-G930 " SEIKO EPSON Co., Ltd. system), be installed to and carry out on printer.The colored ink using can use as described white ink composition, using water as primary solvent, the organic solvent that contains pigment, fixing resin, surfactant, bleeding agent, NMF etc., and contain as required other additive, and use and the ink composite of the look material of corresponding color of all kinds as pigment.As such color ink compositions, for example, there is the color ink compositions of recording in TOHKEMY 2006-282822.

From the above embodiments, according to white degree of screening, the colour gamut on white screen layer when overlapping printing color ink can reproduction range by difference.Therefore, for using the white of white degree of screening of regulation for substrate record color image, prepare the look-up table that is suitable for its white degree of screening in advance, by carry out the record of coloured image with reference to this table, and then can show the suitableeest color in the wide color reproduction region corresponding with white degree of screening.Look-up table is the form of the data of the quantity of ink printing as each data of the view data of the RBG of printing object etc., with printer being set up to corresponding relation, thereby printer show that with reference to look-up table the data of quantity of ink print.The data of the quantity of ink of being exported by this look-up table are to carry out corresponding data with the four corner in the corresponding corresponding color rendering of white degree of screening region.According to the mode of carrying out the record of coloured image with whole and the corresponding corresponding color rendering of white degree of screening region, data are set up to corresponding relation.

In addition, from above-described embodiment, according to white ink composition (white ink), white degree of screening difference.Therefore, for using with the white screen layer of white ink composition printing of regulation for substrate record color image, prepare the look-up table that is suitable for this white ink composition in advance, and by carry out the record of coloured image with reference to this table, and then also can show the suitableeest color in the wide color reproduction region corresponding with white ink composition.The quantity of ink data of being exported by this look-up table are to carry out corresponding data with the four corner in the corresponding corresponding color rendering of white ink region.Carry out the mode of the record of coloured image according to the corresponding color rendering of the white ink with the corresponding region with whole, data are set up to corresponding relation.Thus, even to the identical data of view data of look-up table input, be also different data sometimes from the data of the quantity of ink of corresponding white degree of screening or the different each look-up table output of white ink.

Claims

1. a printed article, is characterized in that, with white degree of screening be more than 50 white ink by recording image in hyaline membrane, described white ink uses white colorant, and and with the resin beyond polyurethane resin and the polyurethane of at least a kind as fixing resin;

Wherein, described white degree of screening is " (L* value-65)/integrated value × 1000 ",

Wherein, integrated value is to be the integrated value of the transmissivity in 380nm～700nm at wavelength, the degree of the catoptrical brightness of L* value representation,

And the resin beyond described polyurethane is at least acrylic acid styrene resin or is at least polyvinyl resin.

2. printed article as claimed in claim 1, is characterized in that, described white degree of screening is more than 70.

3. a recording method, it is characterized in that, when recording colour ink forms on the described image of the printed article described in claim 1 or 2 coloured image, carry out the record of coloured image with reference to the look-up table of the white degree of screening corresponding to regulation or the white ink of regulation.

4. a look-up table, on the described image of printed article claimed in claim 3 recording colour ink form coloured image time use.

5. a white ink, is characterized in that, uses white colorant, and and with the resin beyond the polyurethane resin of at least a kind and polyurethane as fixing resin, the white degree of screening on hyaline membrane when document image is more than 50;